WO2013015315A1 - Film formant barrière contre les gaz et dispositif associé - Google Patents

Film formant barrière contre les gaz et dispositif associé Download PDF

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Publication number
WO2013015315A1
WO2013015315A1 PCT/JP2012/068839 JP2012068839W WO2013015315A1 WO 2013015315 A1 WO2013015315 A1 WO 2013015315A1 JP 2012068839 W JP2012068839 W JP 2012068839W WO 2013015315 A1 WO2013015315 A1 WO 2013015315A1
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film
aluminum oxide
vapor deposition
layer
deposition layer
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PCT/JP2012/068839
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English (en)
Japanese (ja)
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中村　修司
透 北口
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株式会社ダイセル
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Priority to KR1020147003241A priority Critical patent/KR20140048960A/ko
Priority to CN201280037331.1A priority patent/CN103732394A/zh
Publication of WO2013015315A1 publication Critical patent/WO2013015315A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/548—Controlling the composition

Definitions

  • the present invention relates to a film having excellent gas barrier properties (particularly, water vapor barrier properties) and a device comprising this film as a gas barrier member (for example, electronic devices such as liquid crystal elements, thin film solar cell elements, organic EL elements, and electronic paper). About.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2005-178137
  • a barrier vapor deposition layer having a smooth surface is laminated on at least one surface of a base film, and a smooth vapor deposition layer is formed on the barrier vapor deposition layer.
  • a gas barrier film in which an acid-resistant protective layer having a surface is laminated is disclosed.
  • This document describes that an acrylate resin is laminated as a protective layer on a vapor deposition layer.
  • the water vapor permeability achievable with this technique is about 0.1 g / m 2 / day, and the water vapor barrier property is insufficient for use in electronic devices such as organic EL elements and electronic paper.
  • JP 2005-528250 A includes (i) a flexible substrate, (ii) a basic barrier layer deposited on the flexible substrate, and an organic layer deposited on the basic barrier layer.
  • a base stack comprising: (iii) a barrier stack comprising an organic layer deposited on the base stack and deposited on the barrier stack barrier layer; and (iv) a top deposited on the barrier stack.
  • a multilayer barrier coating comprising a separation layer is disclosed. This document describes that the organic layer may contain an acrylate resin.
  • a base stack comprising a base barrier layer and an organic layer deposited on the base barrier layer, and a barrier stack barrier layer deposited on the base stack and an organic layer deposited on the barrier stack barrier layer
  • a high barrier property is obtained by laminating the vapor deposition layer and the organic layer.
  • the process is very complicated, and in order to obtain a water vapor permeability of about 1 ⁇ 10 ⁇ 4 g / m 2 / day, it is necessary to form 10 or more layers, which is not practical.
  • Patent Document 3 discloses that a transparent water vapor barrier film having a barrier film composed of at least an inorganic layer / organic layer / inorganic layer on a resin substrate, the organic layer is acryloyl.
  • a transparent water vapor barrier film mainly composed of a resin obtained by crosslinking a diacrylate having at least one polar group in addition to a group is disclosed.
  • this film still has insufficient water vapor barrier properties.
  • this film can improve transparency by forming an inorganic material layer by vapor deposition and forming an organic material layer on the inorganic material layer by vapor deposition, the productivity is low.
  • a gas barrier film in which a vapor deposition layer containing a metal or a metal compound is laminated on a base film via an acrylic resin layer is also known.
  • JP-A-10-278167 Patent Document 4 discloses a barrier property in which an acrylic resin layer formed by a vacuum ultraviolet ray curing method and a vapor deposition thin film of a metal or a metal compound are sequentially laminated on one surface of a resin film.
  • a laminate is disclosed.
  • acrylic monomers or oligomers are extensively described, and urethane acrylates and silicone acrylates are also exemplified.
  • this barrier laminate cannot yet sufficiently reduce the water vapor permeability, and the gas barrier property cannot be greatly improved.
  • the water vapor permeability (40 ° C., 90% RH) of the barrier laminate is 0.4 g / m 2 / day, which is sufficient for the gas barrier properties required as a device member in recent years. is not.
  • Patent Document 5 discloses that only an acrylic monomer and / or a polymerizable acrylic prepolymer is used as a polymerization component from one side or both surfaces of a flexible base material from the side close to the base material.
  • a gas barrier film that is laminated only repeatedly or twice or more is disclosed.
  • this gas barrier film does not have sufficient water vapor barrier properties.
  • the water vapor permeability (40 ° C., 100% RH) of the gas barrier film is 0.49 g / m 2 / day.
  • the water vapor permeability (40 ° C., 100% RH) is 0.09 g / m 2 / day.
  • Patent Document 6 discloses an inorganic oxide layer (A) on at least a substrate, a (meth) acrylic compound (B) having three or more hydroxyl groups in the molecule, and molecules A laminate in which a (meth) acrylic resin layer (D) containing a (meth) acrylic compound (C) having an alkoxysilyl group therein is laminated is disclosed.
  • a (meth) acrylic resin layer (D) obtained by flash-depositing a (meth) acrylic compound containing 2-methacryloxypropyltrimethoxysilane on a polyethersulfone (PES) film, an oxidation A laminated body is obtained in which three inorganic oxide layers (A) on which aluminum is deposited are alternately and successively stacked.
  • the water vapor permeability (40 ° C., 90% RH) of this laminate is less than 0.01 g / m 2 / day.
  • the gas barrier properties are still not sufficient.
  • Glass also has a very high barrier property. For this reason, at present, it is the only material that meets the requirements for water vapor barrier properties and is transparent for use in electronic devices such as organic EL elements and electronic paper.
  • glass has the disadvantages that it is hard, difficult to bend, and easily broken, and cannot be stored in a roll or used in processes in the processing of electronic devices. For this reason, the use of glass in the manufacture of electronic devices necessitates transportation and processing of the glass cut out one by one while maintaining the flat state, which reduces the productivity of electronic devices.
  • Single crystal aluminum oxide (single crystal sapphire) has a density of about 3.97 g / cm 3 , is transparent, and can achieve a water vapor permeability of about 1 ⁇ 10 ⁇ 4 g / m 2 / day. Therefore, if single-crystal aluminum oxide can be formed on a general-purpose synthetic resin film, it can be a film that is theoretically transparent, flexible, and has high barrier properties.
  • An edge-defined film-fed growth method is known as a typical method for producing single crystal sapphire. In this method, the raw material melt that has risen by a capillary phenomenon through a slit of a mold (die) that defines the crystal shape is crystallized at the upper end of the die. However, since the melting temperature of aluminum oxide exceeds 2000 ° C., there is no synthetic resin that can withstand such a high temperature. Therefore, it has been considered that single crystal aluminum oxide cannot be formed on a synthetic resin film.
  • JP-A-2005-178137 (Claims 1 and 10, paragraph [0037], Examples) JP 2005-528250 A (Claim 1, paragraph [0035]) JP 2004-9395 A (Claims 1 and 2, paragraph [0007]) JP-A-10-278167 (Claim 1, paragraph [0036], Example) Japanese Patent Laying-Open No. 2005-313560 (Claim 1, Paragraph [0033], Example) JP-A-2005-7741 (Claim 1, Example)
  • an object of the present invention is to provide a film having excellent gas barrier properties (particularly water vapor barrier properties) and a device using this film.
  • Another object of the present invention is to provide a film that can achieve both gas barrier properties and transparency and a device using this film.
  • Still another object of the present invention is to provide a film excellent in flexibility and capable of preventing generation of cracks and cracks and a device using this film.
  • Another object of the present invention is to provide a method for easily producing a film having an aluminum oxide vapor deposition layer having a specific composition ratio and / or density in at least a partial region in the thickness direction.
  • Still another object of the present invention is to provide a film that can be suitably used as a gas barrier member of an electronic device.
  • Another object of the present invention is to provide a film that is excellent in adhesion to a solar cell sealant and can be suitably used as a solar cell backsheet.
  • the inventors of the present invention are films in which a vapor-deposited layer of aluminum oxide is formed on at least one surface of a base film via a specific anchor layer, the vapor-deposited layer It was found that a novel film in which aluminum oxide has a specific composition ratio and / or density in at least a partial region in the thickness direction can significantly improve gas barrier properties (particularly, water vapor barrier properties), and thus completed the present invention. .
  • an anchor layer formed of a cured product of a polymerizable composition containing a vinyl compound is laminated on at least one surface of a base film, and a specific vapor deposition made of aluminum oxide is formed on the anchor layer.
  • Layers are stacked.
  • Aluminum oxide has the following characteristics (1) and / or (2) in at least a partial region in the thickness direction of the deposited layer (for example, in the vicinity of the interface with the anchor layer).
  • the peak of the composition ratio (y / x) of aluminum oxide (AlxOy) is 2.1 to 3.0 (for example, 2.2 to 2.8).
  • the density of aluminum oxide is 3. 4 g / cm 3 or more (for example, 3.45 to 3.7 g / cm 3 , preferably 3.5 to 3.6 g / cm 3 ).
  • the structure of aluminum oxide having such a specific composition ratio and / or density is not strictly a sapphire structure because the density of the sapphire crystal structure is 3.97 g / cm 3. It can be called a structure.
  • the density of general aluminum oxide is 3.1 to 3.2 g / cm 3 , whereas it has a density of 3.4 g / cm 3 or more (for example, 3.5 g / cm 3 or more). Therefore, the structure of the aluminum oxide is clearly different from the crystal structure of normal aluminum oxide.
  • the water vapor permeability of the film may be 1 ⁇ 10 ⁇ 3 g / m 2 / day or less.
  • the base film may be made of at least one selected from cyclic polyolefin, polyethylene terephthalate, polyethylene naphthalate, and polyimide.
  • the vinyl compound may contain silicone urethane (meth) acrylate.
  • the arithmetic average roughness (Ra) of the anchor layer may be about 0.1 to 2.0 nm. Silicon atoms may be present in the anchor layer.
  • the thickness of the vapor deposition layer made of aluminum oxide may be about 5 to 100 nm.
  • the present invention also includes a film in which a surface on which an anchor layer of a vapor deposition layer made of aluminum oxide is not formed is subjected to corona treatment or plasma treatment. Moreover, this invention also includes the film in which the vapor deposition layer which consists of silicon oxides was formed on the vapor deposition layer which consists of aluminum oxides. These films are excellent in adhesiveness with a solar cell sealant and can be suitably used as a solar cell backsheet.
  • acrylate and methacrylate are collectively referred to as (meth) acrylate.
  • the upper limit and the lower limit of the numerical range can be arbitrarily combined.
  • the aluminum oxide has a specific composition ratio and / or density in at least a partial region in the thickness direction of the vapor deposition layer
  • gas barrier properties can be remarkably improved.
  • the gas barrier property can be improved even when the thickness of the vapor deposition layer is small or even when a plurality of vapor deposition layers are not formed.
  • gas barrier property and transparency can be made compatible.
  • it is excellent in a softness
  • region can be manufactured simply.
  • the film of the present invention can be suitably used for an electronic device as a gas barrier member, and can effectively prevent deterioration of element performance of the electronic device due to water vapor from the outside.
  • a film in which an aluminum oxide vapor deposition layer is subjected to a specific surface treatment or a film in which a silicon oxide vapor deposition layer is laminated on an aluminum oxide vapor deposition layer has excellent adhesion to a solar cell sealant, and is a solar cell backsheet. It can utilize suitably as.
  • FIG. 1 is a schematic cross-sectional view for explaining a region where aluminum oxide has a specific composition ratio and / or density in the film of the present invention.
  • FIG. 2 is a schematic diagram for explaining the interface between the vapor deposition layer and the anchor layer in the X-ray photoelectron spectroscopy spectrum.
  • FIG. 3 is a schematic cross-sectional view showing an organic EL device provided with the film of the present invention as a gas barrier member.
  • FIG. 4 is a graph showing the results of X-ray photoelectron spectroscopy (XPS analysis) of the film of Example 3.
  • FIG. 5 is a graph showing the results of X-ray photoelectron spectroscopy analysis (XPS analysis) of the film of Comparative Example 4.
  • FIG. 6 is a graph showing the results of X-ray photoelectron spectroscopy analysis (XPS analysis) of the film of Comparative Example 5.
  • FIG. 7 is a graph showing the results of X-ray reflectivity analysis (XRR analysis) of the films of Example 3 and Comparative Examples 4 and 5.
  • the base film is made of plastic (in particular, plastic having a melting point or softening temperature of 300 ° C. or lower).
  • plastic in particular, plastic having a melting point or softening temperature of 300 ° C. or lower.
  • the base film has a melting point or softening temperature lower than the melting temperature of aluminum oxide of 2000 ° C., a sapphire-like structure deposited film can be formed on the base film.
  • the plastic is not particularly limited, and from the viewpoint of heat resistance, for example, cyclic polyolefin (such as homopolymer or copolymer of cyclic olefin such as norbornene), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.) Examples thereof include polyalkylene arylate) and polyimide (transparent polyimide, etc.). These plastics can be used alone or in combination of two or more.
  • cyclic polyolefin such as homopolymer or copolymer of cyclic olefin such as norbornene
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • plastics can be used alone or in combination of two or more.
  • the glass transition temperature (Tg) of the plastic constituting the base film is not particularly limited, and may be, for example, about 40 to 200 ° C., preferably 50 to 180 ° C., and more preferably about 60 to 150 ° C.
  • stabilizers antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.
  • crystal nucleating agents for the base film, stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), crystal nucleating agents, flame retardants, flame retardant aids, fillers, plastics, as necessary.
  • Agents, impact modifiers, reinforcing agents, colorants, dispersants, antistatic agents, foaming agents, antibacterial agents, and the like may be added. These additives can be used alone or in combination of two or more.
  • the base film may be an unstretched film or a stretched (uniaxial or biaxial) film. Further, the surface of the base film may be subjected to surface treatment such as discharge treatment such as corona discharge or glow discharge, acid treatment, and wrinkle treatment in order to improve adhesion.
  • surface treatment such as discharge treatment such as corona discharge or glow discharge, acid treatment, and wrinkle treatment in order to improve adhesion.
  • the total light transmittance of the base film is 80% or more (for example, about 80 to 99.9%), preferably 85% or more (for example, about 85 to 99%), more preferably 90% in accordance with JIS K7105. It may be more (for example, about 90 to 98%).
  • the thickness of the base film may be, for example, about 1 to 500 ⁇ m (for example, 10 to 500 ⁇ m), preferably 10 to 300 ⁇ m, and more preferably about 10 to 200 ⁇ m.
  • the anchor layer is not particularly limited, and is usually formed of a cured product of a polymerizable composition containing a vinyl compound from the viewpoint that a high-density aluminum oxide vapor-deposited thin film can be easily formed.
  • vinyl compounds include monofunctional (meth) acrylates [eg C 1-24 alkyl (meth) acrylate; C 5-10 cycloalkyl (meth) acrylate; bridged cyclic (meth) acrylate; C 6-10 Aryl (meth) acrylate; C 6-10 aryl C 1-4 alkyl (meth) acrylate; hydroxy C 2-10 alkyl (meth) acrylate; poly C 2-4 alkylene glycol mono (meth) acrylate; fluoro C 1-6 Alkyl (meth) acrylate; glycidyl (meth) acrylate, etc.], bifunctional (meth) acrylate [eg, C 2-10 alkanediol di (meth) acrylate; alkanetri to tetraol di (meth) acrylate; poly C 2-4 alkylene Glycol di (meth) acrylate Di (meth) acrylates of C 2-4 alkylene oxide adducts of bis
  • At least urethane (meth) acrylate is preferable from the viewpoint of improving the surface smoothness of the anchor layer and the flexibility of the film.
  • the urethane (meth) acrylate is not particularly limited.
  • the urethane (meth) acrylate has an active hydrogen atom in a polyisocyanate component [or a prepolymer having a free isocyanate group formed by a reaction between a polyisocyanate component and a polyol component] (meta )
  • Urethane (meth) acrylate obtained by reacting acrylate may be used.
  • the polyisocyanate component is not particularly limited as long as it has two or more isocyanate groups in the molecule.
  • aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, heterocyclic polyisocyanate, these Derivatives of polyisocyanates (for example, dimers, trimers, biurets, allophanates of the above polyisocyanates, polymers of carbon dioxide and the above polyisocyanate monomers, carbodiimides, uretdiones, etc.) may also be used.
  • Examples of the silicon-containing polyol include a silicone diol represented by the following formula (1).
  • R 1 to R 4 are the same or different and represent an alkyl group
  • X 1 and X 2 are the same or different and represent an alkylene group
  • n is an integer of 1 or more
  • m1 and m2 Are the same or different and are an integer of 1 or more
  • p1 and p2 are the same or different and are 0 or 1
  • examples of the alkyl group represented by R 1 to R 4 include linear or branched C 1-4 alkyl groups such as methyl, ethyl, propyl, and butyl groups.
  • a preferred alkyl group is a methyl group.
  • urethane (meth) acrylates can be used alone or in combination of two or more.
  • urethane (meth) acrylates urethane (meth) acrylate having a bulky molecular skeleton is preferable from the viewpoint of easily forming a specific crystal structure of aluminum oxide, and the surface smoothness of the anchor layer is improved.
  • At least silicone urethane (meth) acrylate is preferable from the viewpoint that a dense aluminum oxide layer can be easily formed.
  • the number of (meth) acryloyl groups of urethane (meth) acrylate can be selected from the range of about 1 to 20 per molecule, for example, 2 to 18, preferably 3 to 16, and more preferably 4 to 14 (for example, It may be about 6 to 12).
  • the (meth) acryloyl group equivalent of urethane (meth) acrylate may be, for example, about 50 to 800, preferably 70 to 700, and more preferably about 100 to 600.
  • Urethane (meth) acrylate may be a commercially available product (for example, “EBECRYL series” manufactured by Daicel Cytec Co., Ltd.) or prepared by a conventional method (for example, JP-A-2008-74891). May be.
  • the polymerizable composition may contain any component [for example, a polymerization initiator (for example, a photopolymerization initiator such as benzoin), a photosensitizer, a solvent (for example, a hydrocarbon, a halogenated compound). Carbons, alcohols, ethers, esters, ketones, cellosolves, cellosolve acetates, amides, etc.) and additives exemplified in the section of base film (for example, stabilizers, plasticizers, antistatic agents) , Flame retardant, etc.).
  • a polymerization initiator for example, a photopolymerization initiator such as benzoin
  • a photosensitizer for example, a hydrocarbon, a halogenated compound.
  • a solvent for example, a hydrocarbon, a halogenated compound.
  • the polymerizable composition often contains a polymerization initiator and / or a solvent among the optional components.
  • the ratio of the polymerization initiator is about 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably about 0.1 to 2.5 parts by weight with respect to 100 parts by weight of the vinyl compound.
  • the ratio of the solvent may be, for example, about 1 to 500 parts by weight, preferably 10 to 200 parts by weight, and more preferably about 50 to 150 parts by weight with respect to 100 parts by weight of the vinyl compound.
  • the anchor layer is not particularly limited as long as it is composed of a cured product of the polymerizable composition.
  • the anchor layer contains silicon atoms from the viewpoint of improving the gas barrier property (particularly, water vapor barrier property) of the vapor deposition layer. preferable.
  • FIG. 2 is a schematic diagram for explaining the interface between the vapor deposition layer and the anchor layer in the XPS spectrum.
  • the vertical axis represents the ratio of elements present in the vapor deposition layer
  • the horizontal axis represents the depth corresponding to the etching time.
  • the interface between the vapor deposition layer and the anchor layer varies depending on the surface roughness of the anchor layer, and the element ratio of Al and O often varies, but the following thickness position may be used as the interface.
  • the density of aluminum oxide is, for example, 3.4 g / cm 3 or more (for example, 3.4 to 3.9 g / cm 3 ), preferably 3.45 g / cm 3 or more (for example, 3.45 to 3 0.8 g / cm 3 ), more preferably 3.5 g / cm 3 or more (eg, 3.5 to 3.7 g / cm 3 ), usually 3.45 to 3.7 g / cm 3 (eg, 3.5 to 3.6 g / cm 3 ).
  • the composition ratio of aluminum oxide is not particularly limited as long as the above condition (1) is satisfied.
  • the composition ratio of aluminum oxide (ratio of oxygen atoms to aluminum atoms) or the average value thereof is, for example, 1.8 to 3.0 (for example, 1.9 to 2). 0.9), preferably 2.0 to 2.8 (eg, 2.1 to 2.7), more preferably about 2.2 to 2.6 (eg, 2.3 to 2.5). Also good.
  • region of a vapor deposition layer, or its average value is computable by a usual method, for example, XPS analysis.
  • x may be about 1 to 3 (for example, 1 to 2), and y may be about 1 to 4 (for example, 1 to 3).
  • the film of the present invention may have a base film, an anchor layer, and a vapor deposition layer.
  • a vapor deposition layer has a contact site
  • other coating layers are essentially unnecessary.
  • various known coat layers such as a hard coat layer
  • MOCON method that is, water vapor is passed through one surface of a sample (film), dry nitrogen (carrier gas) is passed through the other surface, and a high-sensitivity sensor (coulometric side) on the dry nitrogen side.
  • a method of measuring water vapor passing through a sample by a sensor or the like is widely used.
  • the water vapor permeability can be measured by a conventional apparatus capable of measuring high barrier properties, such as “AQUATRAN” (manufactured by mocon), “Superdetect SKTTW-6-6” (manufactured by TI).
  • the film of the present invention is also excellent in transparency, and the total light transmittance is 80% or more (for example, about 80 to 99.9%), preferably 85% or more (for example, 85 to 90%) in accordance with JIS K7105. About 99%), more preferably 90% or more (for example, about 90 to 98%). Moreover, the film of this invention is excellent in a softness
  • the film of the present invention is not particularly limited as long as an aluminum oxide thin film having a high oxygen ratio and a high density can be formed in a specific region in the thickness direction.
  • polymerization including a vinyl compound on at least one surface of a base film It can be prepared by applying an adhesive composition and then curing to form an anchor layer and depositing aluminum oxide on the anchor layer.
  • the surface of the anchor layer can be smoothed and the crystal growth is promoted so that the anchor layer component and the vapor deposition species interact with each other, or the vapor deposition layer on the anchor layer side forms a specific crystal structure. it can.
  • the vapor deposition layer is formed by a conventional film formation method such as physical vapor deposition (PVD) [for example, vacuum vapor deposition, electron beam vapor deposition, ion beam vapor deposition, ion plating (for example, HCD, electron beam RF, etc.).
  • PVD physical vapor deposition
  • electron beam vapor deposition electron beam vapor deposition
  • ion beam vapor deposition ion plating (for example, HCD, electron beam RF, etc.).
  • the degree of vacuum (or initial degree of vacuum) is about 0.1 ⁇ 10 ⁇ 4 to 100 ⁇ 10 ⁇ 4 Pa, preferably about 1 ⁇ 10 ⁇ 4 to 10 ⁇ 10 ⁇ 4 Pa.
  • an inert gas such as helium, neon, argon, or xenon; air, oxygen, nitrogen, carbon monoxide, carbon dioxide, nitrogen monoxide, sulfur dioxide, or the like can be used.
  • the introduced gas is a mixed gas containing oxygen at a ratio (volume ratio) of about 1 to 50% (preferably 3 to 30%, more preferably 5 to 20%) with respect to the inert gas. Also good.
  • a region having a specific composition ratio and / or density can be formed relatively easily.
  • the applied voltage is, for example, about 0.1 to 100 kV, preferably about 1 to 50 kV.
  • the temperature is usually about 50 to 250 ° C.
  • a region having a specific composition ratio and / or density can be easily formed by applying a relatively large energy by adjusting the applied voltage and / or temperature.
  • Sputtering may be performed using a conventional apparatus (for example, “Quantera SXM” manufactured by PHI).
  • a transparent electrode 35a and an organic light emitting layer 36 are provided at the center of the facing surface.
  • the organic EL element 30 in which the metal electrode 35b and the metal electrode 35b are sequentially stacked is provided, and a pair of gas barrier films are bonded via the adhesive layers 37 at both ends of the organic EL element.
  • gas barrier films having excellent gas barrier properties (particularly, water vapor barrier properties) and transparency are disposed on both sides, so that water vapor can be transmitted from the outside without interfering with light transmittance. Contact with the organic EL element can be prevented, and deterioration of element performance can be effectively prevented.
  • a pair of gas barrier films may oppose on the base film side, and may oppose on the vapor deposition layer side.
  • one or a plurality of (for example, 2 to 4) gas barrier films may be used as long as a part or all of the periphery of the organic EL element is covered with the gas barrier film.
  • Water vapor permeability The water vapor permeability was measured using a water vapor permeability measuring device (“AQUATRAN” manufactured by mocon). Measurement conditions are 40 ° C. and relative humidity 90% RH.
  • Total light transmittance The total light transmittance was measured using a haze meter (NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7105.
  • composition ratio of aluminum oxide The composition ratio of aluminum oxide (the thickness direction of the vapor deposition layer) was measured by an X-ray photoelectron (XPS) spectrum.
  • the XPS analysis was performed by using “QuanteraSXM” manufactured by PHI [X-ray source: monochromated Al (1486.6 eV), detection area: 100 ⁇ m ⁇ , detection depth: about 4 to 5 nm (extraction angle 45 °), measurement spectrum: Al2p , O1s, Si2s, C1s, sputtering conditions: Ar, 2.0 kV, sputtering rate: about 2 nm / min].
  • the density of aluminum oxide was measured by measuring the X-ray intensity profile using “ATX-G” manufactured by Rigaku Corporation under the conditions of counter-cathode: Cu, wavelength: 1.5405 mm, output: 50 kV, 300 mA. Calculations were made by optimizing the simulation parameters to match the profile. As simulation software, “DX-RR3” manufactured by Rigaku Corporation was used.
  • the contact angle was measured according to JIS K2396 using an automatic / dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DCA-VZ type).
  • the tape peel strength was in accordance with JIS Z0237, and an adhesive tape was attached to the surface of the inorganic film, and a 180 ° peel test was performed at a speed of 30 mm / min.
  • Example 1 In a four-necked flask, 320 parts by weight of an isophorone diisocyanate trimer (Perstope, IPDI trimer, Tolonate IDT 70) and 1 part by weight of dibutyltin dilaurate are dissolved in 1 part by weight of acetone and heated to a temperature of 40 ° C. Retained. In this solution, the average composition is
  • the PET film unwound from the roll was applied to a wet (WET) film thickness of 10 ⁇ m, dried by passing through a drying oven at 70 ° C., and then 300 mJ / cm by a metal halide lamp. By irradiating with ultraviolet rays at 2 and curing, the thickness is 5 ⁇ m After forming the anchor layer, it was wound up on a roll to produce a roll film having the anchor layer.
  • WET wet
  • urethane acrylate EBECRYL1290
  • a polymerization initiator Irgacure 184
  • methyl ethyl ketone on the surface opposite to the side on which the anchor layer was formed of the obtained film having an anchor layer.
  • the coating liquid mixed at a ratio of) is applied by a gravure coating method, dried by passing through a drying furnace at 70 ° C., and then cured by irradiating with an ultraviolet ray at 300 mJ / cm 2 with a metal halide lamp. After forming a hard coat layer having a thickness of 5 ⁇ m, it was wound on a roll to produce a roll film having an anchor layer and a hard coat layer.
  • Example 2 A roll film was produced in the same manner as in Example 1 except that a deposited layer having a thickness of 25 nm was formed. The evaluation results of the obtained film are shown in Table 1.
  • Example 3 A roll film was produced in the same manner as in Example 1 except that a vapor deposition layer having a thickness of 20 nm was formed.
  • the evaluation results of the obtained film are shown in Table 1.
  • the XPS analysis of the vapor deposition layer of the obtained film and the XRR analysis result are shown in FIG. 4 and 7, respectively.
  • Comparative Example 1 A roll film was prepared in the same manner as in Example 1 except that silicone diacrylate (manufactured by Daicel-Cytec Co., Ltd., “EBECRYL350”) was used instead of silicone urethane acrylate. The evaluation results of the obtained film are shown in Table 1.
  • Comparative Example 2 A roll film was produced in the same manner as in Example 3 except that silicone diacrylate (EBECRYL350) was used instead of silicone urethane acrylate. The evaluation results of the obtained film are shown in Table 1.
  • Example 3 According to the method of Example 3 described in JP-A-2005-7741, a (meth) acrylic compound having three or more hydroxyl groups in the molecule on a base film (polyethersulfone film, thickness 100 ⁇ m) A (meth) acrylic resin layer (thickness 2 ⁇ m) was formed by flash vapor deposition of a mixture of 20 parts by weight (manufactured by Kyoeisha Chemical Co., Ltd., epoxy ester 80MFA) and 80 parts by weight of 2-methacryloxypropyltrimethoxysilane. A film was prepared by depositing Al 2 O 3 on the (meth) acrylic resin layer by the same sputtering method as in Example 1 to form an inorganic oxide layer (thickness: 20 ⁇ m). The evaluation results of the obtained film are shown in Table 1.
  • Comparative Example 4 A coating liquid prepared by mixing urethane acrylate (EBECRYL1290) as a silicon-free vinyl compound, a polymerization initiator (Irgacure 184), and methyl ethyl ketone at a ratio of 50/1/50 (weight ratio) is obtained by a gravure coating method.
  • PET film Toyobo Co., Ltd., trade name “A4300”, thickness 188 ⁇ m
  • the PET film unwound from the roll was applied on both sides so that the wet (WET) film thickness was 10 ⁇ m, and a 70 ° C. drying oven was applied.
  • an anchor layer having a thickness of 5 ⁇ m and a hard coat layer having a thickness of 5 ⁇ m are formed by irradiating with a metal halide lamp at 300 mJ / cm 2 and curing, and then wound on a roll.
  • Roll film having an anchor layer and a hard coat layer It was produced.
  • the vertical axis represents the ratio of elements present
  • the horizontal axis represents the distance in the thickness direction of the film (depth from the surface) by multiplying the sputtering time by the sputtering rate (2 nm / min). Value.
  • 0 nm of a horizontal axis shows the surface of an aluminum oxide vapor deposition layer.
  • presence of carbon may be shown by contamination, but when it enters into a vapor deposition layer, carbon will naturally lose
  • the vertical axis represents the relative value of the X-ray reflection intensity
  • the horizontal axis represents the X-ray scattering angle.
  • the example has a higher aluminum oxide density and a higher composition ratio than the comparative example.
  • the aluminum oxide is presumed to exist in a state of a mixture of Al 2 O 3 and AlO 2 , aluminum silicate [Al (OH) n (SiOx) m], etc., and the crystal structure changes.
  • a dense film structure is formed. Therefore, the film of an Example has remarkably low water vapor permeability and high transparency compared with the film of a comparative example.
  • Example 4 The average composition is
  • a roll film was prepared in the same manner as in Example 1 except that 240 parts by weight of polydimethylsiloxane represented by the formula (1) was used.
  • the obtained film was formed with a vapor deposition layer having the same composition ratio and density as in Example 1, and showed the same water vapor transmission rate and total light transmittance as in Example 1.
  • Example 5 The average composition is
  • a roll film was produced in the same manner as in Example 1 except that 430 parts by weight of polydimethylsiloxane represented by formula (1) was used.
  • the obtained film was formed with a vapor deposition layer having the same composition ratio and density as in Example 1, and showed the same water vapor transmission rate and total light transmittance as in Example 1.
  • Example 6 The average composition is
  • a roll film was prepared in the same manner as in Example 1 except that 240 parts by weight of polydimethylsiloxane represented by the formula (1) was used.
  • the obtained film was formed with a vapor deposition layer having the same composition ratio and density as in Example 1, and showed the same water vapor transmission rate and total light transmittance as in Example 1.
  • Example 7 The average composition is
  • a roll film was produced in the same manner as in Example 1 except that 430 parts by weight of polydimethylsiloxane represented by formula (1) was used.
  • the obtained film was formed with a vapor deposition layer having the same composition ratio and density as in Example 1, and showed the same water vapor transmission rate and total light transmittance as in Example 1.
  • Example 8 The average composition is
  • a roll film was produced in the same manner as in Example 1 except that 430 parts by weight of polydimethylsiloxane represented by formula (1) was used.
  • the obtained film was formed with a vapor deposition layer having the same composition ratio and density as in Example 1, and showed the same water vapor transmission rate and total light transmittance as in Example 1.
  • Example 9 A roll film having an anchor layer and a hard coat layer was produced in the same manner as in Example 1.
  • Sputtering method [vacuum degree: 5 ⁇ 10 ⁇ 4 Pa, introduced gas: mixed gas of Ar and O 2 (Ar After forming an aluminum oxide [composition AlO] thin film (deposited layer with a thickness of 50 nm) by a volume ratio of O 2 with respect to 15%), a silicon oxide [composition SiO] thin film (with a thickness of 10 nm or less is continuously formed without leaving the chamber) After the vapor deposition layer was formed, the roll film was wound around the roll again with a tensile strength of about 10 kgf. The evaluation results of the obtained film are shown in Table 2.
  • Example 10 A roll film having an anchor layer and a hard coat layer was produced in the same manner as in Example 1. Sputtering method [vacuum degree: 5 ⁇ 10 ⁇ 4 Pa, introduced gas: mixed gas of Ar and O 2 (Ar the O volume ratio of 15% 2) for, after forming an aluminum oxide composition AlO] thin (deposition layer having a thickness of 50 nm), the surface of the aluminum oxide thin film was corona treated, a tensile strength of about 10kgf roll again A roll film was prepared by winding. The evaluation results of the obtained film are shown in Table 2.
  • Example 11 A roll film was produced in the same manner as in Example 5 except that plasma treatment was performed instead of corona treatment. The evaluation results of the obtained film are shown in Table 2.
  • the films of Examples 9 to 11 have higher wettability, a smaller contact angle, and higher tape peel strength than the film of Example 1.
  • the films of Examples 9 to 11 are suitable for uses such as a solar battery back sheet.
  • the film of the present invention has excellent gas barrier properties (particularly water vapor barrier properties) and high transparency.
  • an electronic device for example, a liquid crystal element, a thin film solar cell element, an organic EL element, electronic paper, It can be suitably used for touch panels and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un film possédant une excellente propriété de barrière contre les gaz (en particulier une propriété de barrière contre la vapeur d'eau) ainsi qu'un dispositif mettant en oeuvre ce film. Ce film est obtenu par stratification, au moins sur une des faces du film de base, d'une couche d'ancrage formée au moyen du produit durci d'une composition polymérisable contenant un composé vinyle, et par stratification, sur au moins une partie d'une zone de cette couche d'ancrage et dans le sens de l'épaisseur, d'une couche déposée d'oxyde d'aluminium possédant les caractéristiques (1) et/ou (2) ci-après. (1) Le pic du rapport (x/y) de composition de l'oxyde d'aluminium (AlxOy) est compris entre 2,1 et 3,0. (2) La densité de l'oxyde d'aluminium est supérieure ou égale à 3,4 g/cm3.
PCT/JP2012/068839 2011-07-27 2012-07-25 Film formant barrière contre les gaz et dispositif associé WO2013015315A1 (fr)

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WO2015087949A1 (fr) * 2013-12-11 2015-06-18 凸版印刷株式会社 Corps empilé et film barrière au gaz
CN113699488A (zh) * 2021-07-26 2021-11-26 湖北光安伦芯片有限公司 一种半导体激光器芯片腔面的镀膜方法
JP7334624B2 (ja) 2018-10-18 2023-08-29 東レ株式会社 積層体

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US20140272346A1 (en) * 2013-03-15 2014-09-18 Rubicon Technology, Inc. Method of growing aluminum oxide onto substrates by use of an aluminum source in an oxygen environment to create transparent, scratch resistant windows
WO2015133441A1 (fr) * 2014-03-04 2015-09-11 東洋製罐グループホールディングス株式会社 Stratifié faisant barrière contre les gaz
WO2016098504A1 (fr) * 2014-12-20 2016-06-23 三菱樹脂株式会社 Film d'étanchéité pour éléments électroniques
KR102459495B1 (ko) * 2017-05-30 2022-10-26 리껭테크노스 가부시키가이샤 활성 에너지 경화성 수지 조성물, 하드 코트 적층 필름, 및 유리에 대한 적용을 위한 필름
KR20220024001A (ko) * 2019-06-12 2022-03-03 다이니폰 인사츠 가부시키가이샤 배리어 필름, 적층체 및 포장 제품
WO2022224797A1 (fr) * 2021-04-19 2022-10-27 東レフィルム加工株式会社 Stratifié et procédé de fabrication de stratifié

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WO2015087949A1 (fr) * 2013-12-11 2015-06-18 凸版印刷株式会社 Corps empilé et film barrière au gaz
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